Water-repellent compositions



Patented Sept. 30, 1952 signor to General'Electric Company, a-corporation of New York No Drawing." Application lV Iarch': 1 7, 195 0,

' Serial No. 159,349 4 Claims. (01. 260-29.4).:.

This invention is concerned with compositions of matter suitable for rendering various materials, especially textile materials, water-repellent. More particularly, the invention is concerned with a composition of matter comprising (a) an aminoplast selected from the class consisting of urea-aldehyde and melamine-aldehyde resins or condensation products, (2)) an organopolysiloxane, and (c) the product of hydrolysis of a methyldihalogenosilane corresponding to the general formula CHsSiHXz where X is a halogen.

It has been known heretofore that solid bodies, for example, various textiles, can be rendered Water-repellent by treatment of these materials withan organopolysiloxane. Thus, according to Norton Patent 2,386,259,;various objects can be rendered water-repellent by treating the materials with the product of hydrolysis of a methyldihalogenosilane corresponding to the formula,

mentioned above, It. has also been known as disclosed: in Patriode' Patent 2,306,222, that various objects oanbe rendered Water-repellent by treatment with an organohalogenosilane. The use of various resinous materials in small concentrations has been employed for improving the water repellency of various textiles and increasing their crease resistance; Among such resins may be mentioned, for examples, fcondensation products of urea and an aldehyde as well as condensation products of melamine: and an aldehyde.

'1 have now discovered that unexpectedly I am able to obtain improved water 'repellency, especially on textiles,-by treating the latter with a mixture of ingredients comprising (a) a con- .dens'ation product of either ureaand an aldehyde ,,0r melamine and. an aldehyde, (7)) a liquid organopolysiloxane, and (c) a liquid hydrolysis product of a methyldihalogenosilanesimilar to those described in the aforementioned Norton product of urea or melamine with formaldehyde,

especially the methylol ureas, for instance, di-

. 1. 2 methylol urea, and the methylol melamines, for example, tri-methylol melamine, hexamethylol melamine, etc.

The organopolysiloxanes which may be employed inthe practice of this invention are those which the silicon atoms contain only monothe present invention. Preferably the organopolysiloxane is one in which essentially all the organic groups attached to the silicon atoms are methyl groups, although there may also be pres"- ent other silicon-bonded organic groups, e. g.,

phenyl groups, etc. v

The. methyl hydrogen polysiloxanes employed are those which may be prepared, for instance,

byhydrolyzing a methyl dihalogencsilane of they formula CHsSiI-IXz where X represents a halogen, for instance, chlorine, bromine, etc. Methods for making the oily hydrolysis products of this typeare disclosed more fully in the aforementioned Norton Patent 2,386,359 which'by referenceis made a part of this specification. f

The proportions of urea or melamine. resins, organopolysiloxane, and hydrolysis product of the methyl dihalogenosilane may be varied within fairly wide limits without departing from the scope of the invention. Generally, in a treating mixture on a weight basis, it has been found advantageous that the urea ormelamine resin comprise from about 0.5, to 15 per cent, preferably from. 1 to 10 per cent, and the organopolysiloxane mixture (including the nonhydrogen-containing organopolysiloxane and hydrogen methyl polysiloxane) comprise from 0.5 to 15 per cent, preferably from 1 to 10 per cent, of which from to per cent of the mixture of organopolysiloxanes is the organopolysiloxane free of silicon-bonded hydrogen, and the balance, thatis, from 5 to 25 percent, is the methyl hydrogen polysiloxane, the balance of the treating mixture being made up of either a solvent for the aforementioned ingredients or water, the water acting as a medium in which the other ingredients can be emulsified by use of suitable emulsifying agents. Stated alternatively, and referring specifically to a water emulsion, one range of ingredients which I have found useful comprises from '70 to 98 per cent water, from 0.5 to 15 per cent, by weight, of either the urea or melamine resin, from 0.4 to 12 per cent, by weight, of the organopolysiloxane, andfrom about 0.05-'to3.5 per cent of the methyl hydrogen polysiloxane.

In order to prepare emulsions of the aforemen- 4 this combination of organopolysiloxanes with 2 per cent, by weight (i. e., equal in weight tothe Weight of the mixture of organopolysiloxanes), dim-ethylol urea obtained by condensing urea and formaldehyde, and the rayon and cotton poplin baked for 2 minutes at 150 C. and 1 minute at a 400 Cato, dry the clothiaind cure:the=resin. An-

other-treating sample containin 2z per cent, by weight, of the organopo-lysiloxanes and 4 ,per

tioned ingredients it is desirable to use various ,10 cent dimethylol urea was also applied to the same emulsifying agents (preferablythose whose emul cloths and the latter baked under the same consifying action is destroyed byheat) as, for 'in- -ditions. After-treatment of the cloths, each stance, such materials aslTetrosanmarketedtby cloth was subjected-to a water spray test using Qnyx Chemical Company and-;being'identifiedsas ';the.-method set,- forth in the 1945 Year Book of technical alkyl dimethyl-3,4-dichlorobenzyl am- 15 thefAmerican-Association of Textile Chemists and monium chlorides in which thealkyl groups are Colorists, vol.v 22,, pages 229 to 233. All samples normal primary aliphatic radicals having-from had aspray rating of 100 before laundering and 8 .to 18 carbon atoms, stearamine acetate, etc.' dry-cleaning. The table below shows the spray It will, of course, be apparent to thosesskilledin rating-ofthe samples as treated and after launthe art that any other suitable emulsifying agent 20 dering and after dry-cleaning.

' "Table-I Per Cent of i Cotton Poplin ,Rayon Challis ,Mixture of Dimethyl .PerCent v an: 1' ls A D 1 e i X Y,

fiydroge "Treated Laundered v.Clea ed :Trea ted Laundered Cle ed Silicone v 4 '0 100 70+ 100 .so 100 -2 0 5100- ';70+ -:.s0+ r 50+ 80 0 4 .050 50 -50 -,0 a 0 -50 -0 '2 -=50 50 '50 '0 1 0 ,0 2 ,2 =;-100 00 00+ 100 cs0 100 ,2 1 .4 .100 ,1s0+ 100- n00 90+ -100 -may -be employed without departing from the scope-of the invention.

-Onegeneralprocedure' for making the treating materials employed in the' practice of' my inven- 'tion comprises mixing the required amounts of either the urea or melamine resin with a-c,0ncentrated;organopolysiloxane water emulsion (e. 'g.,

a'35 to 75 per centconcentrationof organopoly- -si1oxane) thereafter adding the methyl, hydro- ,gen, polysiloxane ,to the aforementioned mixture "and thoroughly agitating the combinationtof ingredients :until ;a-,,homogeneous ;emu1sion is formed. This latter emulsion may be diluted further with water to, for instance, concentrations in. the range of from .about:1.0--tof30 per cent preferablyiromfi'to' 10 per cent. I

.In ordenthat those. skilled in the art may, better understand how the, present invention maybe practiced, 'the 'following examples are given'. by

; Way of illustration andnot by way'o'f" limitation. All parts areby weight.

-Inthis examplethe liquid product off hydrolysis" of dimethyldichlorosilane comprising essentially a polymeric 'dimethyls'iloxane was made into-9. per'ce'nt water emulsion (using ste'azramine acetate as the emulsifying agent) There- "after, samples of this emulsion were mixed-with 15 per cent, by weight, of the -hydrolysis --liquid product of methyldichlorosilane, based onthe --weight of 'the dimethylpolysiloxane,- the methyl -hydrogen-polysiloX-anebeing-employed as a 65 per cent by weight,-toluene-solution. A portion-of this mixture wasdiluted with'wate'r to -a='fourper 4 cent polysiloxane concentration and-another-por- -tion-was diluted toa-2 per-cent poly-siloxanecon- 'centration. Rayon and -'c0ttonpop1in- Were treated with these-mixturesaswe11-as with one (2 per 1 cent concentration) mixture comprising From 1 the foregoing-"Tablet 'I,;; it/i-s. a parent: that dimethylol urea-does not-exhibit water-,erepiellent properties when used alone but in combination with the mixture" of dimethyl and methyl'hydro- ,40 "-gensilicones gives:improvedrepellency over that obtained with;thetmixture-of polysiloxanes alone. In'the1treated condition this isbest showzrby the --data--on-rayon where 'Z per 'cent 0f the silicone mixture gives but a 70+ spray rating; while the combination WithfZPGlKZGIlt and 4, percent dimethylol urea-gives a spray rating of "100. With percentdime'thylol urea and 2, per cent otthe "mixtureof organopolysiloXanes the resistance to laundering is superior "to that obtained 'with either 2: per cent-"or '41;per cent of the, mixturejof "dimethyl, and 1 methyl hydrogen ,polys'iloxanes "alone.

"In "this 'example', 2:5 parts of a "vinyl 'acetate emulsion polymer "(Diapene manufacturd by Qua-leer 'ChemicalfProducts Corporation) 3 to 'con- -trolthe handle of the cloth,--were mixed*-with 4 parts-of -awater--soluble "urea-formaldehyde -resin, two parts of =-a'mixture* of -85 per' cent/by weight of =-a rion-volatile dimethyl silicone oil chain stoppered with hexamethyl disiloxane to giveanoil of-about 30-llcentistokesviscosity-(pre- *pare'd in'accordance' with URS. Patent 2,469,888)

and =15 per. cent, by weight, of a product ofhy- 'dro-lysis of -methyldichlorosilane. ,Ihis mixture of ingredients'wasformed into an-emu1sion"by employing an emulsifying agent (Tetrosan "described above) *with- 91-J5 parts water, using the -procedure describedin Example 1. ThiSfCOHJ-POSition was then 'a'ppliedto a-wool rayongabardine an'd the -latter-'dried and-cured 2 minutes-at "33O Z-F. Afteri-al-lowing the cloth to remain -about 1-5 -hours"at-room" temperature, aspray -rating-cf -was -obtained. Another-piece of this-same Spray Rating After Three Launderings Spray Rating After One Dry Cleaning OSriginal P y Rating 2% Silicone-l-Resin 2% Silicone From the foregoing examples it is clearly ap- 7 parent that the combination of the organopolysiloxane, the methyl hydrogen polysiloxane, and the urea-formaldehyde resin is better than either of the ingredients alone when it comes to improving the water repellency properties of the treated textiles. It will, of course, be apparent to those skilled in the art that instead of the cyclic and chain-stoppered methyl polysiloxanes and methyl hydrogen polysiloxane employed in the foregoing examples, other organopolysiloxanes may be used, many of which have been disclosed in the aforementioned Patnode patent as well as in Agens Patent 2,448,756, issued September 7, 1948, without departing from the scope of the invention.

Additionally, instead of the urea formaldehyde resin, other urea-aldehyde resins may be employed, particularly the water-soluble urea-aldehyde resins, and that in place of the urea-aldehyde resins, melamine aldehyde resins may be used, also. Instead of employing an emulsion of the ingredients described above it is also possible to use a solution of the ingredients, for instance, to use an organic solvent which is a solvent for the organopolysiloxane, methyl hydrogen polysiloxane, and the urea or melamine resins. 7

By means of my invention it is possible to improve the water repellency of textiles while at the same time imparting thereto a better crease resistance. The properties of water repellency are not cumulative because of the presence of any one or more of the ingredients but rather unexhyde resins, (b) from 0.4 to 12 percent of an organopolysiloxane free of silicon-bonded hydrogen in which all the organic groups are attached to silicon atoms by carbon-silicon linkages and there are present from 1.9 to 3.0 organic groups per silicon atom, and (c) from 0.05 to 3.5 percent of a methyl hydrogen polysiloxane comprising the liquid product obtained by hydrolyzing methyldichlorosilane, the aforesaid treating composition being in the form of an emulsion of the mixture of polysiloxanes and a water solution of the resinous composition.

2. A composition adapted for rendering textiles water-repellent comprising, by weight, (a) from 0.5 to 15 percent of a water soluble'urea-aldehyde resin, (1)) from 0.4 to 12 percent of an organopolysiloxane free of silicon-bonded hydrogen in which all the organic groups are attached to silicon atoms by carbon-silicon linkages and there are present from 1.9 to 3.0 organic groups per silicon atoms, and (c) from 0.05 to 3.5 percent of a methylhydrogen polysiloxane comprising the liquid product obtained by hydrolyzing methyldichlorosilane, the aforesaid treating composition being in the form of an emulsion of the mixture of polysiloxanes and a water solution of the urea-aldehyde resin.

3. A composition adapted for rendering textiles water-repellent comprising, by weight, (a) from 0.5 to 15 percent of a water soluble melaminealdehyde resin, (2)) from 0.4 to 12 percent of an organopolysiloxane free of silicon-bonded hydrogen in which all the organic groups are attached the malamine-aldehyde resin.

pectedly show an improvement in properties as regards water repellency which is better than the water repellency induced by using any one What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition adapted for rendering textiles water-repellent comprising, by weight, (a) from 0.5 to 15 percent of a resinous composition selected from the class consisting of water-soluble urea-aldehyde and water-soluble melamine-alde- 4. A composition adapted for rendering textiles water-repellent comprising, by weight, (a) from 1 to 10 percent of a water solubleurea-formalde REFERENCES CITED The following references are of record in the file of this patent: v

UNITED STATES PATENTS Number Name Date 2,191,362 Widmer et a1. Feb. 20, 1940 2,386,259 Norton Oct. 9, 1945 2,500,842 MacKenzie et a1. Mar. 14, 1950 2,500,843 MacKenzie et a1. Mar. 14, 1950 2,511,29

Rust June 11, 1950 

1. A COMPOSITION ADAPTED FOR RENDERING TEXTILES WATER-REPELLENT COMPRISING, BY WEIGHT, (A) FROM 0.5 TO 15 PERCENT OF A RESINOUS COMPOSITION SELECTED FROM THE CLASS CONSISTING OF WATER-SOLUBLE UREA-ALDEHYDE AND WATER-SOLUBLE MELAMINE-ALDEHYDR RESINS, (B) FROM 0.4 TO 12 PERCENT OF AN ORGANOPOLYSILOXANE FREE OF SILICON-BONDED HYDROGEN IN WHICH ALL THE ORGANIC GROUPS ARE ATTACHED TO SILICON ATOMS BY CARBON-SILICON LINKAGES AND THERE ARE PRESENT FROM 1.9 TO 3.0 ORGANIC GROUPS PER SILICON ATOM, AND (C) FROM 0.05 TO 3.5 PERCENT OF A METHYL HYDROGEN POLYSILOXANE COMPRISING THE LIQUID PRODUCT OBTAINED BY HYDROLYZING METHYLDICHLOROSILANE, THE AFORESAID TREATING COMPOSITION BEING IN THE FORM OF AN EMULSION OF THE MIXTURE OF POLYSILOXANES AND A WATER SOLUTION OF THE RESINOUS COMPOSITION. 